Premium
TMEDA in Iron‐Catalyzed Kumada Coupling: Amine Adduct versus Homoleptic “ate” Complex Formation
Author(s) -
Bedford Robin B.,
Brenner Peter B.,
Carter Emma,
Cogswell Paul M.,
Haddow Mairi F.,
Harvey Jeremy N.,
Murphy Damien M.,
Nunn Joshua,
Woodall Christopher H.
Publication year - 2014
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201308395
Subject(s) - homoleptic , adduct , chemistry , electrophile , reagent , medicinal chemistry , catalysis , aryl , tetramethylethylenediamine , amine gas treating , yield (engineering) , diamine , polymer chemistry , organic chemistry , materials science , metallurgy , alkyl , metal
The reactions of iron chlorides with mesityl Grignard reagents and tetramethylethylenediamine (TMEDA) under catalytically relevant conditions tend to yield the homoleptic “ate” complex [Fe(mes) 3 ] − (mes=mesityl) rather than adducts of the diamine, and it is this ate complex that accounts for the catalytic activity. Both [Fe(mes) 3 ] − and the related complex [Fe(Bn) 3 ] − (Bn=benzyl) react faster with representative electrophiles than the equivalent neutral [FeR 2 (TMEDA)] complexes. Fe I species are observed under catalytically relevant conditions with both benzyl and smaller aryl Grignard reagents. The X‐ray structures of [Fe(Bn) 3 ] − and [Fe(Bn) 4 ] − were determined; [Fe(Bn) 4 ] − is the first homoleptic σ‐hydrocarbyl Fe III complex that has been structurally characterized.